Monoazo dyestuffs containing a pyridyl group

ABSTRACT

WATER-INSOLUBLE MONOAZO DYESTUFFS OF THE FORMULA:   3-Y,4-(X-(CH2)N-),5-(A-N=N-),6-HO-PYRIDIN-2(1H)-ONE   WHEREIN A IS OPTIONALLY SUBSTITUTED ARYL, N IS 0 OR 1, X IS -CN, -COOR, -COR OR -CONR1R3, Y IS -CN, -COOR, -COR, -CONR1R2 OR ALKYL OR ARYL, R IS OPTIONALLY SUBSTITUTED ALKYL OR ARYL AND R1 AND R2 ARE EACH INDEPENDENTLY HYDROGEN OR OPTIONALLY SUBSTITUTED ALKYL OR ARYL, AND THE USE OF THE DYESTUFFS FOR COLOURING SYNTHETIC TEXITLE MATERIALS.

United States Patent 7 3,657,214 MONOAZO DYESTUFFS CONTAINING A PYRIDYL GROUP Alistair Howard Berrie and Nigel Hughes, Manchester, England, assignors to Imperial Chemical Industries Limited, London, England No Drawing. Filed June 23, 1969, Ser. No. 835,752 Claims priority, application Great Britain, June 27, 1968, 30,761/ 68 Int. Cl. C09b 29/ 36 US. Cl. 260-156 3 Claims ABSTRACT THE DISCLOSURE Water-insoluble monoazo dyestuffs of the formula:

wherein A is optionally substituted aryl, n is 0 or 1, X is CN, COOR, COR or CONR R Y is --CN, -COOR, COR, CONR R or alkyl or aryl, R is optionally substituted alkyl or aryl and R and R are each independently hydrogen or optionally substituted alkyl or aryl, and the use of the dyestuffs for colouring synthetic textile materials.

wherein A is an optionally substituted aryl radical, n is 0 or 1, X is a CN, -COOR, -COR or CONR R radical, Y is a CN, --COOR, COR and -CONR R radical or an alkyl or aryl radical, R is an optionally substituted alkyl or aryl radical, and R and R each independently represent a hydrogen atom or an optionally substituted alkyl or aryl radical or R and R together form with the nitrogen atom a 5- or 6-membered nitrogen-containing heterocyclic ring.

The monoazo dyestuffs of the invention can exist in a number of possible tautomeric forms. For convenience the dyestuffs have only been. formulated in one of these forms, but it is to be understood that the specification relates to the dyestuffs in any of the possible tautomeric forms.

As examples of the optionally substituted aryl radicals represented by A there may be mentioned optionally substituted naphthyl radicals and preferably optionally substituted phenyl radicals, in particular phenyl radicals substituted by one or more of the same or different substituents such as chlorine, bromine, nitro, cyano, lower alkyl such as methyl, lower alkoxy such as methoxy, trifiuoromethyl, lower alkylsulphonyl, lower alkylcarbonyl,

3,657,214 Patented Apr. 18, 1972 carbo lower alkoxy such as carboethoxy which may be substituted by hydroxy or ower alkoxy groups, sulphonsubstituted by hydroxy or lower alkoxy groups, sulphonarnido, carbonamido and N-lower alkyl and N:N-di(lower alkyl) derivatives thereof, di(lower alkyl)amino, phenyl, and phthalyl which is combined with the phenyl radical to form an anthraquinone radical.

Throughout this specification the terms lower alkyl and lower alkoxy are used to denote alkyl and alkoxy radicals respectively containing from 1 to 4- carbon atoms.

The alkyl radicals represented by R, R R and Y are preferably lower alkyl radicals such as methyl, ethyl, npropyl and n-butyl. As examples of the substituted alkyl radicals represented by R, R and R there may be mentioned hydroxy lower alkyl radicals such as fl-hydroxyethyl and ,3- or 'y-(hydroxypropyl), phenyl lower alkyl radicals such as benzyl and B-phenylethyl, lower alkoxy lower alkyl radicals such as B-(methoxy or ethoxy) ethyl, and optionally substituted phenyl radicals such as phenyl itself and tolyl, chlorophenyl, anisyl, bromophenyl and dimethylphenyl.

As examples of the 5- and G-membered nitrogen-containing heterocyclic rings formed by joining together R R and the nitrogen atom there may be mentioned morpholino, piperidino and pyrrolidino.

According to a further feature of the invention there is provided a process for the manufacture of the waterinsoluble monoazo dyestuffs of the invention which comprises coupling a diazo compound of an amine of the formula ANH with a coupling component of the formula:

wherein A, Y, n and X have the meanings stated, the amine and coupling component being free from carboxylic acid and sulphonic acid groups.

The process of the invention can be conveniently carried out by adding the diazo compound, which can for example be in the form of a solution or suspension in an aqueous acidic medium, to a solution or suspension of the coupling component in water and/or a water-soluble organic liquid optionally containing an inorganic acid or an alkali metal hydroxide or carbonate, if necessary adjusting the pH of the mixture to effect coupling, and thereafter isolating the resulting dyestuff by conventional methods.

As examples of the amines of the formula ANH there may be mentioned aniline,

0-, mor p-toluidine,

o, mor p-anisidine,

0-, mor p-chloroaniline, o-, mor pbromoaniline, o-, mor p-nitroaniline, 2: S-dichloroaniline,

2 4-dinitroaniline,

2: 6-dinitroaniline, 2:4-dinitro-6-(chloro or bromo)aniline, 4-methanesulphonylaniline, 4-aminobenzotrifiuoride, 4- or S-nitro-Z-toluidine, 4- or S-nitro-Z-anisidine,

I 4- or S-c'hloro-Z-anisidine,

4- or -chloro-2-toluidine,

4- or 5-bromo-2-anisidine,

2:6-di(chloroor bromo-)-4-nitroaniline,

2:4: 6-trinitroaniline,

2:4-dinitro-6-carbomethoxyaniline,

2-amino-5-nitrobenzotrifiuoride,

2 :4-bis (methanesulphonyl) aniline,

2-(chloroor bromo-)-4-nitroaniline,

methylanthranilate,

4- or S-nitromethylanthranilate,

4-aminobenzamide,

2:6-di(chloroor bromo)-aniline-4-sulphonamide,

2:6-di(chloroor bromo-)-4-methylsulphonylaniline,

2 5-di (chloroor bromo- 4 6-dinitroaniline,

2-amino-3 :S-dinitrobenzotrifiuoride,

3-amino-2-(chloroor bromo-)-4:6-dinitro-(toluene or anisole),

3-arnino-4- (chloroor bromo)-2:6-dinitro(toluene or anisole),

2 or 4-cyanoaniline,

4-nitro-2-cyanoaniline,

2 4-dinitro-6-cyanoaniline,

2-nitro-4-cyanoaniline,

2-chloro-4-cyanoaniline,

3-amino-2z4'z 6-trinitrotoluene,

2-(chloroor bromo-)-4-methylsulphonylaniline,

3-(chloroor bromo-)-4-thiocyanatoaniline,

2-(chloroor bromo-)-4-sulphamylaniline,

Z-aminO-S-nitrophenylmethanesulphone,

2-amino-3 5 -dinitrophenylrnethylsulphone,

2-amino-3- (chloroor bromo-)-5-nitrophenylmethylsulphone,

2-sulpha-myl-4-nitroaniline,

2-ethylsulphamyl-4-nitroaniline,

2-butylsulphamyl-4-nitroaniline,

2-dimethylsulphamyl-4-nitroaniline,

2-methylsulphamyl-4 6-dinitroaniline,

2-methylsulphamyl-4nitro-6-(chloroor bromo-)- aniline,

2-phenylsulphamyl-4-nitroaniline,

methyl 2-amino3-(chloroor brom0-)-5-nitrobenzoate,

ethyl-4-aminobenzoate,

,B-hydroxyethyl-4-aminobenzoate,

fl-methoxyethyl-4-aminobenzoate dimethyl 2-aminoterephthalate,

dimethyl 2-amino-S-nitroterephthalate,

fi- (y8'-ethoxyethoxy) ethyl 4-aminobenzoate,

aniline-2-, 3- or 4-sulphamate,

2-amino-4-chlorophenylsulphamate,

aniline-2-, 3- or 4-N:N-dimethylsulphamate,

4-aminodiphenyl,

l-naphthylamine and 1- or 2-aminoanthraquinone.

The coupling components of Formula I may themselves be obtained by a number of methods such as are described in, for example, Heterocyclic Compounds Pyridine and its DerivativesPart 3, which was edited by Klingsberg and published by Interscience Publishers in 1962. For example by cyclisation of ester, nitrile or NzN- disubstituted amide derivatives of the appropriately a118- substituted glutaconic acid.

As specific examples of the said coupling components there may be mentioned One preferred class of the monoazo dyestuffs of the invention comprises the dyestuffs wherein A is an optionally substituted phenyl radical.

4 A second preferred class comprises the dyestuffs of the formula:

wherein n and X have the meanings stated and A is an optionally substituted phenyl radical.

The water-insoluble monoazo dyestuffs of the invention are valuable for colouring synthetic textile materials, in particular cellulose acetate and cellulose triacetate textile materials, polyamide textile materials such as polyhexamethyleneadipamide textile materials, and preferably aromatic polyester textile materials such as polyethylene terephthalate textile materials. Such textile materials can be in the form of thread, yarn or woven or knitted fabric.

Such textile materials can conveniently be coloured with the monazo dyestuffs, as hereinbefore defined, by immersing the textile material in a dyebath comprising an aqueous dispersion of one or more of the said dyestuffs, which dyebath preferably contains a non-ionic, cationic and/ or anionic surface-active agent, and thereafter heating the dyebath for a period at a suitable temperature. In the case of secondary cellulose acetate textile materials it is preferred to carry out the dyeing process at a temperature between 60 and C.; in the case of cellulose triacetate or polyamide textile material it is preferred to carry out the dyeing process at to C.; in the case of aromatic polyester textile materials the dyeing process can either be carried out at a temperature between 90 and 100 C. preferably in the presence of a carrier such as diphenyl or o-hydroxydiphenyl, or at a temperature above 100 C., preferably at a temperature between and C., under superatmospheric pressure.

Alternatively the aqueous dispersion of the said monoazo dyestulf can be applied to the textile material by a padding or printing process, followed by heating or steaming of the textile material. In such processes it is preferred to incorporate a thickening agent, such as gum tragacanth, gum arabic, or sodium alginate, into the aqueous dispersion of the said monoazo dyestuff.

At the conclusion of the colouring process it is preferred to give the coloured textile material a rinse in water or a brief soaping treatment before finally drying the coloured textile material. In the case of aromatic polyester textile materials it is also preferred to subject the coloured textile material to a treatment in an alkaline aqueous solution of sodium hydrosulphite before the soaping treatment in order to remove loosely attached dyestuff from the surface of the textile material.

The monoazo dyestuffs have excellent affinity and building up properties on synthetic textile materials, and in particular on aromatic polyester textile materials, so enabling heavy depths of shade to be obtained. The resulting colorations which range in shade from yellow to violet, have excellent fastness to light, to wet treatments, and, in particular, to dry heat treatments such as those carried out at high temperatures during pleating operations.

If desired the dyestuffs of the invention can be applied to synthetic textile materials in conjunction with other dispersed dyes, such as are described in, for example, British specifications Nos. 806,271; 835,819; 840,903; 847,175; 852,396; 852,493; 859,899; 865,328; 872,204; 894,012; 908,656; 909,843; 910,306; 913,856; 919,424; 944,513; 944,722; 953,887; 595,816; 960,235 and 916,412.

The invention is illustrated but not limited by the following example in which the parts are by weight:

EXAMPLE 1 5 parts of a aqueous solution of sodium nitrite are added with stirring to a solution of 2.16 parts of 6 aniline 3-NzN-dimethylsulphamate in a mixture of 50 pling components listed in the third column of the table parts of Water and 2.5 parts of a concentrated aqueous using methods similar to that described in Example 1.

solution of hydrochloric acid, at a temperature between The fourth column of the table indicates the shades oband C., and the mixture is stirred for minutes at tained when the dyestuffs are applied to polyester textile the same temperature. 5 materials.

The resulting solution of the diazo compound is added Ethyl 2:6-dihydroxy-3-cyanopyrid-4-ylacetate and 2:6- during 15 minutes to a solution of 2.25 parts of ethyl dihydroxy-3-cyano-4-carboethoxypyridine were obtained 2:6-dihydroxy-3-cyanopyrid-4-ylacetate and 5 parts of by the methods described in volume 65 of the Journal of sodium acetate in 110 parts of a 0.8% aqueous solution the American Chemical Society at page 449.

of sodium hydroxide, the temperature being maintained 1O 2:6-dihydroxy-3-cyano-4-cyanomethylpyridine was obbetween 0 and 5 C. by external cooling. The mixture tained by condensing ethyl-3-oxo-4cyanobutanoate with is stirred for a further 15 minutes, acidified with acetic cyanacetamide in the presence of piperidine.

acid, and the precipitated dyestuff is filtered off, washed 2:6-dihydroxy-3-cyano-4- (benzoylmethyl or p-methoxywith water and dried. benzoylmethyDpyridine were obtained by condensing Amine Coupling component Shade 2-oh1or0aniline Ethyl 2:6-dihydroxy-3-eyanopyrid-4ylacetate GreeniSh-yellow. 4-ehloroaniline do Do. 2-nitr0aniline. Do. 3-nitroaniline D0. 4-nitroaniline. Do. Z-anisidine Reddish-yellow. 4-toluidine Yellow. Ethyl 4-an1inoben e- Greenish-yellow. B-Methoxyethyl 3 amino o. l-naphthylamine Reddish-yellow. l-aminoanthraqnino D0 4-aminodiphenyl Yellow. Aniline do Do. 4-1nethyl-2-nitroaniline do Reddish-yellow. 4-methoxy-2-nitroaniline Orange. 4-chlor0-2-nitroani1ine. Greenlsh-yellow. 2-chloro-4-nitroanili'ne Do. 4-cyanoaniline o. 4-dimethylaminoanilin Violet 2 4-dichloroauiline 2: 5-dichloroaniline 2:4:6-trichloroaniline. 2:4:6-trichloroanil1'ne. 4-ehloroaniline 2-nitroaniline ....do 2:6-dihydr0xy-3cyano-4-(carbo-Bethoxyethoxy)pyridine Do. 2-nitroaniline. Do.

do 2:fi-dihydroxy-3-eyano-4-benzoylmethyl pyridine D0. 4-chloroan1lme 0 Do. .do 2:6%11hydr0xy-3-cyano-4-(p-methoxybenzoylmethyl) py11d11l6 Do. 2-nitroanil1ne. do '.l Do. o 2:6-dihydroxy-3-cyano-4(carbamoylmethyl)pyridine Do. 4-ehloroaniline Do. o 2:6-d1hydroxy-3-cyano-4-(N-ethylcarbamoyhnethyl) pyridine- Do. 2-nitr0ani1ine Do. o 2:6-d1hydr0Xy-3-cyano4-(N :N-diethylearbamoylmethyl)pyridine-.. Du. 4-chloroaniline do Do.

o 2:6-dihydr0Xy-3-cyano-t-(N-phenylcarbamoylmethyl)pyridine Do.

2-nitroaniline. Do.

Ethyl 4-aminobenzoate- Do. 4-methOXy-2-nil;r0aniline Orange. 4-chloroaniline 2:6-dihydroxy-3-cyano-4-(N-p-methoxyphenylcarbamoylmethyl)pyridine-... Greenish-yellow 2nitroamiline do Do.

o 2:6-dihydr0xy-3-eyano-4-(N-piperidin-1-yl-earbonylmethyl)pyridine Do. 48 4-ehl0r0aniline do iv Do. 49 o Ethyl 2:6-dihydr0Xy-3-aeetylpyrid-l-ylacetate Do. 50 Z-nitroaniline -do Do. 51 d Ethyl :fi-dihydroxy-B-carboethoxypyrld-4-yl-acetate go. 52 o o. 53 Ethyl 2:6-dihydr0xy-3-carbamoylpyrid-4-yl-acetate 150- 54. e o 0. 55 t-chloroaniline Ethyl 2:6-dihydroxy-B-methylpyrldA-ylacetate Do. 56. Ethyl l-aminobenmato Do. 57- 4-methoxy-2-nitroaniline do Orange. 58 4-nitroaniline Ethyl 2:6 dihydroxy-3-phenylpyrid-4-ylacetate Greenish-yellow. b9 4-rnethyl-2-nitroaniline do Reddish-yellow. 60. 2-bromo-4-nitroaniline Ethyl 2:6-dihydroxy-3-cyanopyrid-4-ylaeetate Grcenish-yellow. 61 4-methylsulphonylaniline Do. 62. Anilinet-sulphonamide Do. 63 t-aminobenzamide Do. 64 t-acetylaniline -do Do. 65 Z-trifluoromethylaniline- Do. 66 4-acetylaminoaniline Reddrsh-yellow. 67. B-nitroaniline Greemsh-yellow. 68. Z-chloroaniline Do. 69. o D0. 70. 2-nitro-4-methoxyaniline Orange. 71 4-nitroaniline Greenrsh-yellow.

3-chlor0aniline- Do.

4-aminobenzamide- Do. 2-bromo-4-nitroaniline D0. 2-nitroaniline 6 -4 Do.

2:4-dichloroanil d Do.

When dispersed in aqueous medium the dyestuff dyes ethyl-3-oxo-4-(benzoyl or p-methoxybenzoyl)butadiene aromatic polyester textile materials in deep greenishwith cyanacetamideinthe presence of piperidine.

yellow shades of excellent fastness properties. Ethyl 2:6-dihydroxy-3-cyanopyrid-4-ylacetate on reac- The following table gives further examples of the dyetion with amomnia, ethylamine, diethylamine, aniline, pstulfs of the invention which are obtained by diazotising anisidine and piperidine gave the corresponding 4-carbamthe amines listed in the second column of the table and oylmethyl compounds.

coupling the resulting diazo compounds with the cou- 75 Ethyl 2:6-dihydroxy-3-acetylpyrid-4-ylacetate was obtained by condensing ethylacetonedicarboxylate with acetoacetamide in the presence of triethylamine.

Ethyl 2:6-dihydroXy-3carboethoxypyrid-4 ylacetate was obtained by condensing together equimolecular proportions of ethylacetone dicarboxylate, diethylmalonate and ammonia in the presence of triethylamine.

Ethyl 2:6-dihydroxy-3carbarnoylpyrid-4-ylacetate was obtained by condensing ethylacetone dicarboxylate with malonodiamide in the presence of piperidine.

Ethyl 2:6-dihydroxy-3-(methyl or pheny1)pyrid-4-ylacetate were obtained by cyclisation of fl-(methyl or phenyl)[i-ethoxycarbonylmethylglutaconamide in sulphuric acid.

2:6-dihydroxy-3-cyano 4 carboethoxypyridine on transesterification with B-ethoxyethanol gave 2:6-dihydroxy-3-cyano-4-(carbo-B-ethoxyethoxy)pyridine.

2:6 dihydroxy-3cyano-4-phenoxycarbonylpyridine was obtained by transesterification of 2:6-dihydroxy-3-cyano 4-carboxypyridine with phenol.

2:6 dihydroxy-3 :4-dicyanopyridine was obtained by dehydration of 2:6-dihydroXy-3-cyano-4carbamoylpyridine using P205.

2:6 dihydroxy 3 N ethylcarbamoyl-4-(N-ethylcarbamoylmethyhpyridine was obtained by heating ethyl 2:6- dihydroxy-3carboethoxypyrid 4 ylacetate with ethylamine; and the same ester on transesterification with phenol afiorded 2:6-dihydroxy-3 phenoxycarbonyl 4- (phenoxycarbonylmethyl pyridine.

2:6-dihydroxy-3benzoyl-4-carboethoxypyridine was obtained by treating ethyl citrazinate with benzoylchloride in the presence of aluminium chloride.

We claim:

1. Water-insoluble monoazo dyestuif free from sulphonic acid and carboxylic acid groups having the general formula (C Ha) "X wherein A is selected from the group consisting of phenyl, naphthyl and phenyl substituted with a member selected from the group consisting of chlorine, bromine, nitro, cyano, lower alkyl, lower alkoxy, trifluoromethyl, lower alkylsulphonyl, lower alkycarbamyl, carbo lower alkoxy, sulphonamido, N-lower alkyl sulphonamido, NzN-di (lower alkyl) sulphonamido, carbonamido, N-lower alkyl carbonamido, N:N-di(lower alkyl)carbonamido, di(lower alkyl)amino, phenyl and phthalyl; n is an integer of 01; X is selected from the group consisting of CEN, COR and CONR R Y is selected from the group consisting of CEN, COOR, COR, -CONR R lower alkyl and phenyl; R is selected from the group consisting of lower alkyl, hydroxy lower alkyl, lower alkoxy lower alkyl, pheny and methoxypheny; and R and R each independently are selected from the group consisting of hydrogen, lower alkyl, phenyl and methoxyphenyl and R and R together with the nitrogen atom to which they are attached form the ring selected from the group consisting of morpholino, piperidino and pyrrolidino rings.

2. The water-insoluble monoazo dyestuff of claim 1 wherein R and R together with the nitrogen atom to which they are attached form the piperidino ring.

3. The water-insoluble monoazo dyestufl of claim 1 having the formula wherein A, X and n have the meaning given in claim 1.

References Cited UNITED STATES PATENTS 3,487,066 12/1969 Ritter et a1. 260l56 JOSEPH REBOLD, Primary Examiner D. M. =PAPUGA, Assistant Examiner U.S. Cl. X.R.

2602472 A, 293.69, 294.9, 295.5 A, 295.5 R, 296 R 

